%0 Journal Article
%T Capturing Enzyme-Loaded Diblock Copolymer Vesicles Using an Aldehyde-Functionalized Hydrophilic Polymer Brush.
%A Karchilakis G
%A Varlas S
%A Johnson EC
%A Norvilaite O
%A Farmer MAH
%A Sanderson G
%A Leggett GJ
%A Armes SP
%J Langmuir
%V 40
%N 27
%D 2024 Jul 9
%M 38934738
%F 4.331
%R 10.1021/acs.langmuir.4c01561
%X Compared to lipids, block copolymer vesicles are potentially robust nanocontainers for enzymes owing to their enhanced chemical stability, particularly in challenging environments. Herein we report that cis-diol-functional diblock copolymer vesicles can be chemically adsorbed onto a hydrophilic aldehyde-functional polymer brush via acetal bond formation under mild conditions (pH 5.5, 20 °C). Quartz crystal microbalance studies indicated an adsorbed amount, Γ, of 158 mg m-2 for vesicle adsorption onto such brushes, whereas negligible adsorption (Γ = 0.1 mg m-2) was observed for a control experiment conducted using a cis-diol-functionalized brush. Scanning electron microscopy and ellipsometry studies indicated a mean surface coverage of around 30% at the brush surface, which suggests reasonably efficient chemical adsorption. Importantly, such vesicles can be conveniently loaded with a model enzyme (horseradish peroxidase, HRP) using an aqueous polymerization-induced self-assembly formulation. Moreover, the immobilized vesicles remained permeable toward small molecules while retaining their enzyme payload. The enzymatic activity of such HRP-loaded vesicles was demonstrated using a well-established colorimetric assay. In principle, this efficient vesicle-on-brush strategy can be applied to a wide range of enzymes and functional proteins for the design of next-generation immobilized nanoreactors for enzyme-mediated catalysis.